WO2012041994A1 - Improved method for isomerisation of hop alpha-acids to iso-alpha-acids - Google Patents
Improved method for isomerisation of hop alpha-acids to iso-alpha-acids Download PDFInfo
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- WO2012041994A1 WO2012041994A1 PCT/EP2011/067055 EP2011067055W WO2012041994A1 WO 2012041994 A1 WO2012041994 A1 WO 2012041994A1 EP 2011067055 W EP2011067055 W EP 2011067055W WO 2012041994 A1 WO2012041994 A1 WO 2012041994A1
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12C—BEER; PREPARATION OF BEER BY FERMENTATION; PREPARATION OF MALT FOR MAKING BEER; PREPARATION OF HOPS FOR MAKING BEER
- C12C3/00—Treatment of hops
- C12C3/12—Isomerised products from hops
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- the present invention relates to an improved process for the production of iso-alpha-acids (isohumulones) by the isomerisation of hop alpha-acids (humulones), such as in the form of a hop extract, using carbon-containing chemical compounds (or mixtures thereof) with one or more functional groups containing a (basic) nitrogen atom with a lone electron pair (a lone electron pair is a valence electron pair without bonding or sharing with other atoms).
- the present invention further relates to iso-alpha-acid compositions obtained by said improved isomerisation process and to the use of said iso-alpha-acid compositions in food and beverage application, particularly as bittering formulation, and/or as source to obtain reduced or hydrogenated iso-alpha-acid compositions.
- hops in the form of hop cones or hop pellets, are added during the wort boiling stage of the brewing process.
- alpha-acids humulones, such as humulone, adhumulone, cohumulone, posthumulone and prehumulone
- iso-alpha-acids are responsible for the characteristic bitter taste of hopped beer.
- Typical alpha-acid levels in the wort at the start of the wort boiling are below 0.01 wt% (below 100 ppm).
- hop utilization could be improved by performing the alpha-acid isomerisation outside the brewing process, and particularly under the effect of basic inorganic compounds.
- One patent uses powdered hops as process feed which are mixed with alkaline earth metal oxides and subsequently heated under anaerobic conditions (US 4,123,561 ). Disadvantages of this process are off-flavour formation and low hop utilization. Therefore, the later developments used hop extracts, obtained by extraction of hop resins (among others the alpha-acids) from the hop cones, rather than powdered hops.
- hop extracts instead of the traditional hop products has multiple advantages, among which a more stable and more consistent chemical composition.
- hop extracts are nowadays obtained via liquid or supercritical carbon dioxide extraction, which eliminates the problems of the presence of pesticide and solvent residues in the extracts experienced before when applying organic extraction solvents like hexane.
- Carbon dioxide hop extracts provide predominantly alpha-acids (humulones) next to beta-acids (lupulones), and they can be further fractionated to obtain alpha-acid enriched hop extracts.
- the "off-line" pre-isomerisation of alpha- acids outside the brewing (wort boiling) process can be achieved using alkali metal and/or alkaline earth metal based compounds via two approaches.
- the first approach applies a solvent-free reaction medium while in the other approach the transformation is performed after addition of solvents, either pure water or alternatively water mixed with an organic solvent.
- the first approach is generally based on alkaline earth metal compounds, for example alkaline earth metal oxides (e.g. MgO). These inorganic accelerators are mixed with the alpha-acid containing extract. However, during these isomerisation processes, the oxides are at least partially dissolved and therefore, after a long reaction time at elevated temperature, the iso-alpha-acid products are obtained as alkaline earth metal cation - isohumulate complexes (US 5,015,491 ) with an isomer distribution of cis- and frans-iso-alpha-acids of 50:50. To obtain the iso-alpha-acids as an organic phase, an additional step is required which involves acidification (with e.g.
- alkali metal salts and/or alkaline earth metal salts are used, e.g. K 2 C0 3 and MgCI 2 solutions (US 3,765,903; US 3,952,061 ; US 4,002,683; US 4,758,445).
- Stoichiometric quantities of alkali metal cations and high temperatures are generally required to convert the alpha-acids into iso-alpha-acids in the water containing reaction medium.
- an acidification and a decantation step are required.
- the presence of water leads to the formation of unwanted degradation by-products, e.g. humulinic acids.
- an alkaline earth metal salt e.g. MgS0 4
- an alkali metal salt K 2 C0 3
- the present invention provides an improved process for the isomerisation of hop alpha-acids (or (partially) hydrogenated alpha-acids, particularly tetrahydro-alpha-acids) to iso-alpha- acids (or (partially) hydrogenated iso-alpha-acids, particularly tetrahydro-iso-alpha-acids) using carbon-containing chemical compounds having one or more functional groups containing a (basic) nitrogen atom with a lone electron pair.
- the present invention further relates to iso-alpha-acid compositions obtainable by said isomerisation of the present invention, and the use thereof.
- a first object of the present invention provides a process for the isomerisation of hop alpha- acids to hop iso-alpha-acids comprising mixing a hop alpha-acid containing feed with at least one carbon-containing chemical compound with one or more functional groups containing a (basic) nitrogen atom with a lone electron pair and thus subjecting the hop alpha-acids to isomerisation.
- said hop alpha-acid containing feed is a hop extract, more preferably being obtained by extraction with liquid or supercritical carbon dioxide.
- said carbon-containing chemical compound with one or more functional groups containing a (basic) nitrogen atom with a lone electron pair is selected from the group consisting of amino acids, ester compounds derived from an amino acid, amide compounds derived from an amino acid, salt compounds derived from an amino acid, amino phenols, amino alcohols, amino sugars, amines, imines, oximes, hydroxylamines, amidines, guanidines, amides, imides, ureas, pyrimidines, purines, and (functionalized) oligomeric or polymeric derivatives of these compounds; and these compounds are non-cyclic (aliphatic or unsaturated carbon side chains), cyclic (saturated or unsaturated rings), or heterocyclic (saturated or unsaturated rings) molecules.
- zwitterionic carbon-containing chemical compounds with one or more functional groups containing a (basic) nitrogen atom with a lone electron pair have at least one functional group containing a (basic) nitrogen atom with a pKb value below 6, more preferably have at least one functional group containing a (basic) nitrogen atom with a pKb value below 5, most preferably at least one functional group containing a (basic) nitrogen atom with a pKb value below 4.
- non-zwitterionic carbon-containing chemical compounds with one or more functional groups containing a (basic) nitrogen atom with a lone electron pair comprise preferably at least one nitrogen atom that is bound to two or three carbon atoms, as for example in the case of secondary and tertiary amino groups.
- Said non-zwitterionic carbon-containing chemical compounds with one or more functional groups containing a (basic) nitrogen atom with a lone electron pair have preferably at least one functional group containing a (basic) nitrogen atom with a pKb value below 9, more preferably at least one functional group containing a (basic) nitrogen atom with a pKb value below 7, most preferably at least one functional group containing a (basic) nitrogen atom with a pKb value below 5.
- said carbon-containing chemical compound with one or more functional groups containing a (basic) nitrogen atom with a lone electron pair is a compound generally present in beer products and/or naturally occurring in the human body. More preferably said carbon-containing chemical compound with one or more functional groups containing a (basic) nitrogen atom with a lone electron pair is an alpha amino acid with D-stereoisomer configuration, an alpha amino acid with L- stereoisomer configuration, a beta amino acid, or a gamma amino acid. Most preferably, said carbon-containing chemical compound with one or more functional groups containing a (basic) nitrogen atom with a lone electron pair is L-proline or beta-alanine.
- the alpha-acid isomerisation reaction occurs under an oxygen-free atmosphere.
- the concentration of the alpha-acid compounds in the reaction medium i.e. after addition of the carbon-containing chemical compound with one or more functional groups containing a (basic) nitrogen atom with a lone electron pair to the alpha-acid containing feed, at the start of the isomerisation reaction is at least 1 weight%.
- the alpha-acid isomerisation reaction occurs in solvent-free or non-aqueous conditions.
- the alpha-acid isomerisation reaction according to the present invention when the used carbon-containing chemical compound with one or more functional groups containing a (basic) nitrogen atom with a lone electron pair is not an amino acid, may be performed in a solvent or in a mixture of solvents.
- the mass ratio of said amino acid to water in the reaction medium is preferably at least 5:1 .
- the pH of the reaction medium for the alpha-acid isomerisation is at least > 5.5, preferably > 6.5, more preferably > 7.0, most preferably > 7.5.
- the alpha-acid isomerisation reaction occurs at a temperature of at least 278 K, more preferably at a temperature between 323 and 383 K.
- the alpha-acid isomerisation reaction is performed at a molar ratio of alpha-acid to the nitrogen content of said chemical compound with one or more functional groups containing a (basic) nitrogen atom with a lone electron pair between 20:1 and 1 : 10 at the start of the isomerisation reaction.
- Another preferred embodiment provides a method for the isomerisation of hop alpha-acids comprising mixing a hop alpha-acid containing feed with at least one carbon-containing chemical compound with one or more functional groups containing a (basic) nitrogen atom with a lone electron pair and further comprising a hydrogenation and/or reduction reaction step.
- said hydrogenation and/or reduction reaction is carried out in the presence of hydrogen with heterogeneous metal based catalysts, preferably noble metal based catalysts, either in the absence or in the presence of a solvent, at a temperature of at least 278 K.
- a second object of the present invention provides a hop iso-alpha-acid composition prepared or preparable from a hop extract comprising isomerised hop alpha-acids and at least one carbon-containing chemical compound having one or more functional groups containing a (basic) nitrogen atom with a lone electron pair.
- the molar ratio of iso-alpha-acid to the nitrogen content of said carbon-containing chemical compound(s) with one or more functional groups containing a (basic) nitrogen atom with a lone electron pair of said hop iso- alpha-acid composition is between 20:1 and 1 :10.
- said hop iso-alpha-acid composition comprises iso-alpha-acid compounds and L-proline with a molar ratio of iso- alpha-acid to L-proline is between 3:1 and 1 :3.
- Said iso-alpha-acid composition according to the present invention may comprise hop iso-alpha-acid compounds that are partially or fully reduced and/or hydrogenated.
- a third object of the present invention relates to the use of a hop iso-alpha-acid composition according to the present invention in food, beverage or beer applications, particularly as bittering formulation for beer and beverage products. Also, said hop iso-alpha-acid composition according to the present invention can be used as feed for hydrogenation and/or reduction processes to yield partially or fully hydrogenated or reduced iso-alpha-acids.
- a "lone electron pair” is a valence electron pair without bonding or sharing with other atoms.
- amino acid is a molecule containing an amino group, a carboxylic acid group and a (side) chain that varies between different amino acids.
- an alpha amino acid the amino group is attached to the carbon atom immediately adjacent to the carboxylic acid group (the alpha carbon).
- the various alpha amino acids differ in the kind of side chain attached to their alpha carbon, and can vary in size from just one hydrogen atom in glycine to a large heterocyclic group in tryptophan.
- Other types of amino acids exist when the amino group is attached to a different carbon atom; for example, in a beta amino acid (such as e.g.
- beta- alanine the amino group is at the beta position from the carboxylic acid group, while in a gamma amino acid (such as e.g. gamma-amino-butyric acid) the carbon atom to which the amino group attaches is separated from the carboxylic acid group by two other carbon atoms.
- a gamma amino acid such as e.g. gamma-amino-butyric acid
- alpha-acid includes any alpha-acid compound naturally present in hop or a hop extract, such as humulone, adhumulone, cohumulone, posthumulone and prehumulone, as well as a hydrogenated and/or reduced derivative thereof, including a dihydro- and tetrahydro-alpha-acid compound, preferably a tetrahydro-alpha-acid.
- iso-alpha- acid includes any compound that is an isomerised hop alpha-acid compound, such as isohumulone, iso-adhumulone, iso-cohumulone, iso-posthumulone and iso-prehumulone, as well as a hydrogenated and/or reduced derivative thereof, including a dihydro-iso-alpha-acid, a tetrahydro-iso-alpha-acid and a hexahydro-iso-alpha-acid compound.
- isomerised hop alpha-acid compound such as isohumulone, iso-adhumulone, iso-cohumulone, iso-posthumulone and iso-prehumulone
- a hydrogenated and/or reduced derivative thereof including a dihydro-iso-alpha-acid, a tetrahydro-iso-alpha-acid and a hexahydro-iso-alpha-acid compound.
- the present invention provides an improved process for the isomerisation of hop alpha-acids (or (partially) hydrogenated alpha-acids, particularly tetrahydro-alpha-acids) to iso-alpha- acids (or (partially) hydrogenated iso-alpha-acids, particularly tetrahydro-iso-alpha-acids) using carbon-containing chemical compounds having one or more functional groups containing a (basic) nitrogen atom with a lone electron pair.
- the isomerisation of hop alpha-acids to iso-alpha-acids is catalyzed upon addition of these carbon-containing chemical compounds with one or more functional groups containing a (basic) nitrogen atom with a lone electron pair (or a mixture thereof) to the hop alpha-acid containing feed.
- the present invention further relates to iso-alpha-acid compositions obtainable by said alpha-acid isomerisation of the present invention, and the use thereof.
- a first object of the present invention relates to a method for the isomerisation of hop alpha-acids (or (partially) hydrogenated alpha-acids) comprising contacting or mixing an alpha-acid containing feed, preferably a hop extract, and a carbon-containing chemical compound with one or more functional groups containing a (basic) nitrogen atom with a lone pair (or mixtures of such compounds), either in the absence or in the presence of a solvent, preferably at a reaction temperature of at least 278 K, and preferably in the absence of oxygen.
- the alpha-acid containing feed is preferably a hop extract, said hop extract preferably obtained by liquid or supercritical carbon dioxide extraction.
- the alpha-acid containing feed can be a feed of pure hop alpha-acids, or a hop extract enriched in hop alpha-acids, or a mixture of hop alpha-acids and hop beta-acids, or a mixture of hop alpha-acids, hop beta-acids and hop oils, or a mixture of hop alpha-acids, hop beta-acids, hop oils and hop hard resins, or a hop extract, or a carbon dioxide hop extract.
- the alpha-acid containing feed can also be hop pellets or powdered hops.
- an alpha-acid containing feed that (naturally) contains a carbon-containing chemical compound with one or more functional groups containing a (basic) nitrogen atom with a lone electron pair, as may be the case if powdered hops or hop pellets are used as the alpha-acid containing feed.
- a carbon dioxide hop extract on the other hand, the content of for example the naturally occurring alpha amino acids with L-stereoisomer configuration is very low as amino acids (and also oligopeptides and polypeptides) are almost insoluble in dense carbon dioxide and are thus not extracted during the hop acid extraction process.
- said carbon- containing chemical compound with one or more functional groups containing a (basic) nitrogen atom with a lone electron pair is added to the hop alpha-acid containing feed, in addition to one or more of said carbon-containing chemical compounds with one or more functional groups containing a (basic) nitrogen atom with a lone electron pair that may already naturally be present.
- Carbon-containing chemical compound with one or more functional groups containing a (basic) nitrogen atom with a lone electron pair can be, but is not limited to an amino acid, amino phenol, amino alcohol, amino sugar, amine, imine, oxime, amide, imide, urea, hydroxylamine, amidine, guanidine, purine, pyrimidine, or a (functionalized) derivative thereof, or can also be an oligomeric or polymeric compound (e.g an oligopeptide or polypeptide/protein) containing at least one (basic) nitrogen atom with a lone electron pair.
- Said compound can structurally be a non-cyclic (aliphatic or unsaturated carbon side chains), cyclic (saturated or unsaturated rings), or heterocyclic (saturated or unsaturated rings) molecule.
- said carbon-containing chemical compound with at least one functional group containing a (basic) nitrogen atom with a lone electron pair can exist as a zwitterion (such as amino acids e.g. alpha amino acids with L-stereoisomer configuration or beta amino acids like beta-alanine).
- Said zwitterionic carbon-containing chemical compound with at least one functional group containing a (basic) nitrogen atom with a lone electron pair thus comprises, apart from other functional groups, at least the combination of an acidic centre (such as a carboxylic acid group) and a basic centre (amino group).
- a preferred zwitterionic carbon-containing chemical compound with at least one functional group containing a (basic) nitrogen atom with a lone electron pair is an amino acid with only one (basic) nitrogen atom with a lone electron pair (e.g. glycine, L-proline and beta-alanine), more preferably is an alpha amino acid, most preferably the L-stereoisomer thereof, with a non-polar side chain (for example L-proline) or with a polar, uncharged side chain (for example L-threonine).
- Another preferred zwitterionic carbon-containing chemical compound according to the present invention is an amino acid, more preferably an alpha amino acid, most preferably the L-stereoisomer thereof, with at least two (basic) nitrogen atoms with a lone electron pair (for example L-tryptophan).
- Said zwitterionic carbon-containing chemical compounds with one or more functional groups containing a (basic) nitrogen atom with a lone electron pair have preferably at least one functional group containing a (basic) nitrogen atom with a pKb value below 6 (for example L- asparagine), more preferably at least one functional group containing a (basic) nitrogen atom with a pKb value below 5 (for example L-alanine), most preferably at least one functional group containing a (basic) nitrogen atom with a pKb value below 4 (for example L-proline).
- said carbon-containing chemical compound with at least one functional group containing a (basic) nitrogen atom with a lone electron pair cannot exist as a zwitterion.
- said non-zwitterionic carbon-containing chemical compounds with one or more functional groups containing a (basic) nitrogen atom with a lone electron pair of comprise at least one nitrogen atom that is bound to two or three carbon atoms, as for example in the case of secondary and tertiary amino groups.
- non-zwitterionic carbon-containing chemical compounds with one or more functional groups containing a (basic) nitrogen atom with a lone electron pair have preferably at least one functional group containing a (basic) nitrogen atom with a pKb value below 9 (for example pyridine), more preferably at least one functional group containing a (basic) nitrogen atom with a pKb value below 7 (for example purine), most preferably at least one functional group containing a (basic) nitrogen atom with a pKb value below 5 (for example piperidine).
- said carbon-containing chemical compound with one or more functional groups containing a (basic) nitrogen atom with a lone electron pair is a safe compound that has GRAS status, and/or is a compound that is naturally occurring in the human body or that is generally present in beverages, particularly beer products.
- Such preferred carbon-containing chemical compounds with one or more functional groups containing a (basic) nitrogen atom with a lone electron pair include among others the naturally occurring amino acids, for example (alpha) amino acids such as glycine, L-proline, beta-alanine, gamma-amino-butyric acid, ornithine, etc., More preferably, said carbon-containing chemical compound with one or more functional groups containing a (basic) nitrogen atom with a lone electron pair is an alpha amino acid, most preferably with the L-stereoisomer configuration, more in particular selected from the group consisting of L- alanine, L-valine, L-leucine, L-isoleucine, L-phenylalanine, L-tryptophan, L-methionine, L- proline, L-aspartic acid, L-glutamic acid, L-glutamine, L-serine, L-threonine, L-cysteine, L- t
- the iso-alpha-acid product obtained by performing the method according to the present invention wherein one or more naturally occurring compounds (such as the naturally occurring (alpha) amino acids, for example L-amino acids (e.g.
- L-proline are used as the carbon-containing chemical compound(s) with a functional group containing a (basic) nitrogen atom with a lone electron pair for the alpha-acid isomerisation reaction, can be applied as such, or alternatively diluted in a food- or beer-compatible solvent (e.g. water and/or ethanol), in food and beverages applications, particularly for beers, particularly as a bittering formulation, without requiring additional purification prior to use.
- a food- or beer-compatible solvent e.g. water and/or ethanol
- the iso-alpha-acid products can be (partially) separated from the carbon-containing chemical compound(s) with one or more functional groups containing a (basic) nitrogen atom with a lone electron pair by means of separation techniques such as washing, extraction, etc.
- said carbon-containing chemical compound with one or more functional groups containing a (basic) nitrogen atom with a lone electron pair is an amino acid of the alpha-amino-acid-type with a D-stereoisomer configuration, more preferably selected from the group consisting of D-alanine, D-valine, D- leucine, D-isoleucine, D-phenylalanine, D-tryptophan, D-methionine, D-proline, D-aspartic acid, D-glutamic acid, D-glutamine, D-serine, D-threonine, D-cysteine, D-tyrosine, D- asparagine, D-histidine D-lysine, D-arginine and D-selenocysteine.
- said carbon-containing chemical compound with one or more functional groups containing a (basic) nitrogen atom with a lone electron pair is an amino acid with the amino group not in alpha position of the carboxylic acid group, including but not limited to an amino acid of the beta-am ino-acid-type like beta-alanine, niacin (vitamin B3), etc., or an amino acid of the gamma-amino-acid type like gamma-amino-butyric acid.
- said carbon-containing chemical compound with one or more functional groups containing a (basic) nitrogen atom with a lone electron pair is an ester compound derived from an amino acid, e.g. an ester compound formed by reaction of L- or D-amino acids with ethanol (for example L-proline ethyl ester), or formed by reaction of beta-alanine with ethanol, etc.
- said carbon-containing chemical compound with one or more functional groups containing a (basic) nitrogen atom with a lone electron pair is an amide compound derived from an amino acid, e.g. the amide compounds formed by reaction of L- or D-amino acids with amine compounds (for example L- prolinamide), etc.
- said carbon-containing chemical compound with one or more functional groups containing a (basic) nitrogen atom with a lone electron pair is a salt compound derived from amino acids, for example monosodium glutamate, monopotassium glutamate, etc.
- said carbon-containing chemical compound with one or more functional groups containing a (basic) nitrogen atom with a lone electron pair is an amino alcohol (i.e. a carbon-containing chemical compound with at least one or more functional groups containing a (basic) nitrogen atom with a lone electron pair and at least one alcohol group, apart from other functional groups), for example L-prolinol, sphingosine and its derivatives (sphingolipids), tris(hydroxymethyl)aminomethane, triethanolamine, etc.
- said carbon-containing chemical compound with one or more functional groups containing a (basic) nitrogen atom with a lone electron pair is an amino sugar or its derivatives, for example meglumine, glucosamine (and polymeric derivatives thereof such as chitosan), riboflavin (vitamin B2) and nucleosides.
- said carbon-containing chemical compound with one or more functional groups containing a (basic) nitrogen atom with a lone electron pair is a nitrogen-containing oligomer or polymer, for example oligopeptides, polypeptides, glycoproteins, melanoidins, polyvinylpyrrolidone, polyethyleneimine, etc.
- said carbon-containing chemical compound with one or more functional groups containing a (basic) nitrogen atom with a lone electron pair is selected from amines, hydroxylamines, ureas, purines, pyrimidines, azoles, imines, oximes, amides, imides, amidines, guanidines.
- These compounds can be non-cyclic (aliphatic or unsaturated carbon side chains), or cyclic (saturated or unsaturated rings) or heterocyclic (saturated or unsaturated rings).
- examples are pyridine, piperidine, pyrrolidine, pyrazine, piperazine, pyrimidine(s), (imid)azole(s), purine(s), picolines, lutidines, etc. and their derivatives.
- the alpha-acid isomerisation reaction is catalyzed upon addition of mixtures of the above described carbon-containing chemical compound(s) with one or more functional groups containing a (basic) nitrogen atom with a lone electron pair.
- a hop alpha-acid isomerisation process according to the present invention is performed at oxygen levels in the atmosphere above the reaction mixture lower than 5 %, 4 %, 3 %, 2 % or 1 %. More preferably, during a hop alpha-acid isomerisation process according to the present invention an oxygen-free or inert atmosphere is maintained above the reaction mixture. Suitable inert or oxygen-free atmospheres can be created by using gases like nitrogen, helium, argon or carbon dioxide, or by working under vacuum.
- the isomerisation reaction according to the present invention can be performed in solvent-free conditions, or in the presence of a solvent or mixture of solvents.
- isomerisation of alpha-acids using said above described carbon-containing chemical compound with one or more functional groups containing a (basic) nitrogen atom with a lone electron pair is performed in solvent-free conditions, such as in the case when mixing said above described carbon-containing chemical compound with a hop extract obtained by liquid or supercritical carbon dioxide extraction, or in non-aqueous conditions when performed in the presence of a solvent or a mixture of solvents.
- the isomerisation of alpha-acids according to the present invention can be performed in the presence of a protic solvent (for example with hydroxyl groups), including H 2 0, EtOH, etc. or mixtures thereof.
- a protic solvent for example with hydroxyl groups
- the pH of the reaction medium for the alpha-acid isomerisation is at least > 5.5, preferably > 6.5, more preferably > 7.0, most preferably > 7.5. It is thus understood that a method for isomerisation of hop alpha-acids according to the present invention typically takes place under conditions different from the wort boiling stage of the brewing process, with a typical pH of about 5.2.
- the alpha-acid isomerisation according to the present invention using a carbon-containing chemical compound with one or more functional groups containing a (basic) nitrogen atom with a lone pair is preferably performed in reaction mixtures, which can be solvent-free or can comprise one or more solvents, with an alpha-acid content of at least 0.5 weight%, 1 weight% or 2 weight% at the start of the isomerisation reaction.
- the yield of iso-alpha-acids in the alpha-acid isomerisation by means of a carbon-containing chemical compound with one or more functional groups containing a (basic) nitrogen atom was the same as in the control experiment performed in the absence of a carbon-containing chemical compound with one or more functional groups containing a (basic) nitrogen atom.
- the alpha-acid isomerisation according to the present invention using a zwitterionic carbon- containing chemical compound with one or more functional groups containing a (basic) nitrogen atom with a lone pair is preferably performed in the absence of H 2 0 in the reaction mixture or with a low content of H 2 0 in the reaction mixture. More preferably, the mass ratio of the zwitterionic carbon-containing chemical compound with one or more functional groups containing a (basic) nitrogen atom with a lone pair to H 2 0 in the reaction mixture is at least 3:1 , 5:1 , 7:1 or 10:1.
- the alpha-acid isomerisation reaction according to the present invention is allowed to proceed for a time sufficient to achieve more than 50 %, 60 %, 70 % or 80 % conversion of the alpha-acid reactants, more preferably at least 90 % conversion of the alpha-acid reactants, with preferably more than 90 % selectivity to iso-alpha-acid products.
- the reaction time to obtain at least a 50 %, 60 %, 70 %, 80 % or 90 % yield of iso-alpha-acids is, given a specific alpha-acid containing feed (with a specific composition and alpha-acid content), inter alia dependent on the used carbon-containing chemical compound(s) with one or more functional groups containing a (basic) nitrogen atom with a lone electron pair, on the applied substrate to said carbon-containing chemical compound(s) with one or more functional groups containing a (basic) nitrogen atom with a lone electron pair ratio, and on the applied process conditions such as the reaction temperature and the presence or absence of solvents or solvent mixtures.
- the alpha-acid isomerisation is performed with the molar ratio of the alpha-acid to the nitrogen content of the carbon-containing chemical compound(s) with one or more functional groups containing a (basic) nitrogen atom with a lone electron pair between 20:1 and 1 :10, preferably between 10:1 and 1 :5 or between 5:1 and 1 :5, more preferably between 3:1 and 1 :3 or between 2:1 and 1 :2 at the start of the isomerisation reaction.
- the isomerisation of hop alpha-acids to iso-alpha-acids according to the present invention is performed at reaction temperatures of at least 278 K.
- the alpha-acid isomerisation of hop alpha-acids to iso-alpha-acids according to the present invention.
- isomerisation is performed at a reaction temperature in the range of 293 K to 388 K, more preferably in the range of 323 K to 383 K, most preferably in the range of 353 K to 378 K.
- the hop alpha-acid isomerisation according to the present invention is preferably performed with reaction times in the range of 0.1 to 48 hours, more preferably in the range of 0.5 to 24 hours, most preferably in the range of 1 to 12 hours.
- the concentration of the carbon-containing chemical compounds with one or more functional groups containing a (basic) nitrogen atom with a lone electron pair in the iso-alpha-acid containing product phase can be lowered, or the iso-alpha-acid products can be separated, via separation techniques such as extraction, washing or more advanced separation techniques known in the art.
- the beer-compatible carbon-containing chemical compound(s) with one or more functional groups containing a (basic) nitrogen atom with a lone electron pair in particular those that are generally present in beer products and/or naturally occurring in the human body, such as amino acids, particularly beta-alanine or alpha-amino acids with an L-stereoisomer configuration, like L- proline, are not removed from the iso-alpha-acid product phase after the isomerisation reaction.
- the present invention also relates to a method for the preparation of derived
- hop alpha-acids comprising the step of mixing a hop alpha-acid containing feed and a carbon-containing chemical compound with one or more functional groups containing a (basic) nitrogen atom with a lone electron pair acting (or a mixture of said compounds), either in the absence or in the presence of a solvent and preferably in the absence of oxygen, and, optionally, further comprising the step of a hydrogenation and/or reduction reaction by performing a hydrogenation and/or reduction reaction of the alpha-acids and/or iso-alpha-acids.
- Said hydrogenation and/or reduction reactions can be any process which results in the formation of dihydro-, tetrahydro-, and/or hexahydro-iso-alpha-acids.
- Many hydrogenation and/or reduction processes are well known in the art. For instance, all reduction processes known in the art for the production of dihydro-iso-alpha-acids (or hexahydro-iso-alpha-acids via a tetrahydro-iso-alpha-acid intermediate) use a borohydride mediated reduction of iso- alpha-acids or derivatives thereof (US 3,558,326; US 4,324,810).
- the hydrogenation processes to produce tetrahydro-iso-alpha-acids are carried out in the presence of H 2 with heterogeneous noble metal catalysts, generally based on Pd (US 5,013,571 ; US 5,600,012).
- said hydrogenation processes are carried out in the presence of H 2 with metal based catalysts, such as based on (noble) metals.
- These hydrogenation processes are carried out in the presence of H 2 with catalysts based on for example Ag, Au, Co, Cu, Ir, Ni, Pd, Pt, Rh, Ru, etc.
- the combination of the alpha-acid isomerisation with a hydrogenation reaction results in the formation of hexahydro-iso-alpha-acids, but does not require an additional reduction reaction, such as an alkali metal borohydride reduction.
- the present invention also relates to a method for the derivatization of alpha-acids comprising the steps of
- iso-alpha- acids are obtained that are rich in cs-iso-alpha-acids, which are more chemically stable than frans-iso-alpha-acids.
- the invention allows to obtain iso-alpha-acids with a cis:trans ratio that is preferably is equal to or higher than 65:35, more preferably that is equal to or higher than 70:30, and most preferably that is equal to or higher than 75:25.
- the present invention thus relates to a method for the production of an iso-alpha-acid composition, with a cis:trans ratio of preferably at least 65:35, more preferably at least 70:30 or most preferably at least 75:25, comprising the steps of (i) mixing an alpha-acid containing feed and a carbon-containing chemical compound with one or more functional groups containing a (basic) nitrogen atom with a lone electron pair (or a mixture of said compounds), either in the absence or in the presence of a suitable solvent and preferably in the absence of oxygen, and (ii) subjecting said reaction mixture to a temperature of at least 278 K.
- the alpha-acid isomerisation reaction according to the present invention can be carried out without, and does not require, the addition of inorganic compounds as isomerisation accelerators, like soluble alkali metal or alkaline earth metal compounds, such as those used in the isomerisation reactions known in the art.
- inorganic compounds like soluble alkali metal or alkaline earth metal compounds, such as those used in the isomerisation reactions known in the art.
- sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, magnesium oxide, calcium oxide, sodium carbonate, potassium carbonate, magnesium carbonate, calcium carbonate, sodium bicarbonate, potassium bicarbonate, magnesium bicarbonate or calcium bicarbonate is not limitative.
- the alpha-acid isomerisation process according to the present invention can be conducted in a batch reactor whereby the carbon-containing chemical compound with one or more functional groups containing a (basic) nitrogen atom with a lone electron pair (or a combination of such compounds) and an alpha-acid containing feed are loaded into the reaction vessel at the start of the process. It is also possible to use other reactor procedures and designs (for example also for continuous mode processes) that are generally known to people skilled in chemical processes.
- a second object of the present invention provides an iso-alpha-acid composition obtainable by the methods according to the present invention, wherein said iso-alpha-acid composition comprises iso-alpha-acid compounds with a cis:trans ratio of preferably at least 65:35, more preferably of at least 70:30 or most preferably at least 75:25.
- said iso-alpha-acid composition preferably prepared from a hop extract, comprises one or more iso-alpha-acid compounds (hydrogenated or not and/or reduced or not) and one or more carbon-containing chemical compounds with one or more functional groups containing a (basic) nitrogen atom with a lone electron pair.
- said iso-alpha-acid composition is a liquid iso-alpha-acid composition.
- Said carbon- containing chemical compound with one or more functional groups containing a (basic) nitrogen atom with a lone electron pair can be any of the above described carbon-containing chemical compounds with one or more functional groups containing a (basic) nitrogen atom with a lone electron pair, but preferably said carbon-containing compound is a safe compound with GRAS status, and/or is a compound that is naturally occurring in the human body or that is generally present in beverages, particularly beer products, such as the naturally occurring amino acids, in particularly the alpha amino acids with L-stereoisomer configuration.
- the molar ratio of the iso-alpha-acid to the nitrogen content of an amino acid or another carbon-containing chemical compound with one or more functional groups containing a (basic) nitrogen atom with a lone electron pair is between 20:1 and 1 :10, preferably between 10:1 and 1 :5 or between 5:1 and 1 :5, more preferably between 3:1 and 1 :3 or between 2:1 and 1 :2.
- said iso-alpha-acid composition comprises one or more iso-alpha-acid compounds
- amino acid (hydrogenated or not and/or reduced or not) and an amino acid with a molar ratio of iso- alpha-acid to said amino acid between 3:1 and 1 :3, most preferably between 2:1 and 1 :2.
- amino acid is L-proline or beta-alanine.
- the iso-alpha-acid composition according to the present invention can be used as process feed for hydrogenation and/or reduction processes to yield hydrogenated or reduced iso- alpha-acids, such as dihydro-iso-alpha-acids, tetrahydro-iso-alpha-acids, hexahydro-iso- alpha-acids, etc.
- the iso-alpha-acid products can be separated from the iso- alpha-acid composition according to the present invention by means of separation techniques such as washing, extraction or more advanced procedures, etc., and
- said carbon-containing chemical compound with one or more functional groups containing a (basic) nitrogen atom with a lone electron pair according to the present invention is not separated from said iso-alpha-acid composition before the hydrogenation and/or reduction reaction.
- the present invention also relates to an iso-alpha-acid composition obtainable by the methods according to the present invention, wherein said iso-alpha-acid composition comprises iso-alpha acid compounds with a cis:trans ratio (of the iso-alpha-acid isomers and/or hydrogenated or reduced iso-alpha-acid compounds) of preferably at least 65:35, more preferably at least 70:30.
- a cis:trans ratio of the iso-alpha-acid isomers and/or hydrogenated or reduced iso-alpha-acid compounds
- said iso-alpha-acid composition comprises iso-alpha-acid compounds and/or hydrogenated or reduced iso-alpha-acid compounds, such as dihydro-iso-alpha-acids, tetrahydro-iso-alpha-acids and/or hexahydro- iso-alpha-acids.
- said iso-alpha-acid composition comprises one or more iso-alpha- acid compounds (hydrogenated or not and/or reduced or not) and one or more carbon- containing chemical compounds with one or more functional groups containing a (basic) nitrogen atom with a lone electron pair.
- Said carbon-containing chemical compound with one or more functional groups containing a (basic) nitrogen atom with a lone electron pair can be any of the above-described carbon-containing chemical compounds with one or more functional groups containing a (basic) nitrogen atom with a lone electron pair.
- said iso-alpha-acid composition comprises one or more iso-alpha-acid compounds derived from hop products (hydrogenated or not and/or reduced or not) and one or more carbon-containing chemical compounds with one or more functional groups containing a (basic) nitrogen atom with a lone electron pair that are naturally occurring in the human body and/or generally present in beer products, such as the naturally occurring amino acids, particularly the alpha amino-acids with L-stereoisomer configuration, like L-proline.
- the iso-alpha-acid products (hydrogenated or not and/or reduced or not) can be separated from the iso-alpha-acid composition according to the present invention by means of separation techniques such as washing, extraction or more advanced procedures, etc.
- Said iso-alpha-acid composition (comprising one or more iso-alpha-acid compounds
- the carbon- containing chemical compound (or mixture thereof) with one or more functional groups containing a (basic) nitrogen atom with a lone electron pair according to the present invention is not separated from the iso-alpha-acid compounds (hydrogenated or not and/or reduced or not).
- Example 1 Solvent-free isomerisation of alpha-acids ⁇ alpha-acid feed containing alpha-acids and iso-alpha-acids) with carbon-containing chemical compounds with one or more functional groups containing a (basic) nitrogen atom with a lone pair at 363 K
- the sample analyses were performed by means of an HPLC device equipped with a binary pump, vacuum degasser, autosampler, column thermostat, and diode array detector. Two Zorbax Extend C18 columns (150 mm length ⁇ 4.6 mm inner diameter, packed with 5 ⁇ particles) were used in series.
- the mobile phase consisted of 5 mM ammonium acetate in 20 % (v/v) ethanol adjusted to a pH of 9.95 with ammonia (A solvent) and a mixture consisting of 60 % acetonitrile (60 %) and 40 % ethanol (v/v) (B solvent).
- the flow rate was set at 0.4 imL/min and solvent gradient elution was performed: 0 - 12 min: 0 - 16 % B, 12 - 14 min: 16 - 25 % B, 14 - 44 min: 25 - 40 % B, 44 - 54 min: 40 - 60 % B, 54 - 64 min: 60 - 90 % B, 64 - 70 min: 90 - 100 % B.
- the column temperature was maintained at 308 K. 100 ⁇ _ volumes of filtered samples were injected.
- the UV detection was performed at 256 nm for the iso-alpha- acid products and 330 nm for the alpha-acid substrates.
- the samples from the solvent-free isomerisation experiments were analyzed after addition of 1 imL ethanol.
- Example 2 Solvent-free isomerisation of alpha-acids ⁇ alpha-acid feed: hop extract enriched in alpha-acids) with carbon-containing chemical compounds with one or more functional groups containing a (basic) nitrogen atom with a lone pair at 363 K
- Example 4 Solvent-free isomerisation of alpha-acids (alpha-acid feed: hop extract enriched in alpha-acids) with carbon-containing chemical compounds with one or more functional groups containing a (basic) nitrogen atom with a lone pair, as part of a functional group in the carbon-containing chemical compound or apart from other functional groups in the carbon- containing chemical compound, at 363 K
- Example 2 The isomerisation experiments were performed as described in Example 2.
- the starting composition of the alpha-acid feed was: 94.1 % alpha-acids and 5.9 % iso-alpha-acids. 0.36 g of alpha-acid feed was added to a 1 mL volume of a solvent or a solvent mixture. After addition of L-proline, the reaction mixture was stirred and heated to 363 K for 6 h. All reaction vessels were pressurized with 2.0 MPa nitrogen gas.
- Example 2 For the sample analyses, the same HPLC procedure was applied as described in Example 1 , except for the sample preparation. The samples were analyzed after dilution in a 5 mL ethanol volume.
- Example 6 Isomerisation of alpha-acids (alpha-acid feed: hop extract enriched in alpha- acids) in the presence of solvents with carbon-containing chemical compounds with one or more functional groups containing a (basic) nitrogen atom with a lone pair at 363 K
- Example 2 For the sample analyses, the same HPLC procedure was applied as described in Example 1 , except for the sample preparation. The samples were analyzed after fivefold dilution of the reaction mixture in ethanol.
- alpha-acid feed hop extract enriched in alpha-acids
- solvents with carbon-containing chemical compounds with one or more functional groups containing a (basic) nitrogen atom with a lone pair at 363 K
- the starting composition of the alpha-acid feed was: 94.1 % alpha-acids and 5.9 % iso-alpha-acids.
- reaction mixture were stirred and heated to 363 K for reaction times of 6 h and 20 h. All reaction vessels were pressurized with 0.2 MPa nitrogen gas.
- Example 1 except for the variations in reaction temperature (348 K, 363 K and 378 K instead of 363 K), reaction time (2 h, 6 h and 8 h instead of 6 h) and molar reactant:L-proline ratio (1 , 2 and 4 instead of 1 ).
- iso-alpha-acid yields of 23.1 % (Table 8, entry 3) and 16.9 % (Table 8, entry 4) were obtained for molar reactant:L-proline ratios of respectively 2 and 4.
- Example 9 Solvent-free isomerisation of alpha-acids with carbon-containing chemical compounds with one or more functional groups containing a (basic) nitrogen atom with a lone pair at 363 K: determination of cis:trans ratio and long-term stability of iso-alpha-acid products
- the UPLC device comprised a binary pump, vacuum degasser, autosampler, column thermostat, and diode array detector.
- One Acquity HSS C18 column (150 mm length x 2.1 mm inner diameter, packed with 1 .8 ⁇ particles) was used.
- the mobile phase consisted of water acidified to a pH of 2.8 with phosphoric acid (A solvent) and acetonitrile (B solvent).
- the flow rate was set at 0.5 imL/min and isocratic solvent gradient elution was performed: 48 % A and 52 % B.
- the column temperature was maintained at 308 K. 5 ⁇ volumes of filtered samples were injected.
- the UV detection was performed at 270 nm.
- the samples from the solvent-free isomerisation experiments were analyzed after 100-fold dilution with 0.5 % H 2 S0 4 in methanol.
- HPLC and UPLC analysis revealed that, after 50 days of cool storage (278 K), the fraction of c s-iso-alpha-acids in the iso-alpha-acid product pool was still > 75 %.
- Example 10 Hydrogenation of the reaction product phase obtained from the solvent-free isomerisation of alpha-acids with carbon-containing chemical compounds with one or more functional groups containing a (basic) nitrogen atom with a lone pair
- the iso-alpha-acid reactant feed used in this example was a mixture of L-proline and iso- alpha-acids, which contained 0.36 g of iso-alpha-acids.
- This feed mixture was prepared following the procedure of Table 8, entry 8.
- reaction mixture was stirred and heated to 348 K, for a reaction time of 24 h for the hydrogenation experiments with the Ru containing catalyst and for 20 h for the hydrogenation experiments with the Pd based catalyst. All reaction vessels were pressurized with 2.0 MPa hydrogen gas. After the hydrogenation reaction, the powder catalysts (Ru/C and Pd/C) were separated from the reaction mixture by centrifugation.
- the sample analyses were, after separation of the hydrogenation catalysts from the reaction mixture, performed as described in Example 1 , and the UV detection of the tetrahydro-iso- alpha-acids and hexahydro-iso-alpha-acids was also performed at 256 nm.
Abstract
Description
Claims
Priority Applications (14)
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RU2013108177/04A RU2573635C2 (en) | 2010-09-30 | 2011-09-29 | Improved method of isomerisation of hop alpha-acids into iso-alpha-acids |
CA2808980A CA2808980A1 (en) | 2010-09-30 | 2011-09-29 | Improved method for isomerisation of hop alpha-acids to iso-alpha-acids |
EP20110767226 EP2622060B1 (en) | 2010-09-30 | 2011-09-29 | Improved method for isomerisation of hop alpha-acids to iso-alpha-acids |
SI201130561T SI2622060T1 (en) | 2010-09-30 | 2011-09-29 | Improved method for isomerisation of hop alpha-acids to iso-alpha-acids |
UAA201304104A UA109671C2 (en) | 2010-09-30 | 2011-09-29 | Normal;heading 1;heading 2;heading 3;IMPROVED METHOD FOR ISOMERISATION OF HOP ALPHA-ACIDS TO ISO-ALPHA-ACIDS |
MX2013002693A MX2013002693A (en) | 2010-09-30 | 2011-09-29 | Improved method for isomerisation of hop alpha-acids to iso-alpha-acids. |
AU2011310098A AU2011310098B2 (en) | 2010-09-30 | 2011-09-29 | Improved method for isomerisation of hop alpha-acids to iso-alpha-acids |
BR112013006406A BR112013006406A2 (en) | 2010-09-30 | 2011-09-29 | improved method of isomerization of hop alpha acids to iso-alpha acids |
PL11767226T PL2622060T3 (en) | 2010-09-30 | 2011-09-29 | Improved method for isomerisation of hop alpha-acids to iso-alpha-acids |
NZ607511A NZ607511A (en) | 2010-09-30 | 2011-09-29 | Improved method for isomerisation of hop alpha-acids to iso-alpha-acids |
CN201180046369.0A CN103180428B (en) | 2010-09-30 | 2011-09-29 | Hops alpha-acid is isomerizated into improving one's methods of iso-alpha-acid |
ES11767226.1T ES2545130T3 (en) | 2010-09-30 | 2011-09-29 | Improved method for isomerization of hop alpha acids to iso alpha acids |
US13/876,915 US9909088B2 (en) | 2010-09-30 | 2011-09-29 | Method for isomerisation of hop alpha-acids to iso-alpha-acids |
DK11767226.1T DK2622060T3 (en) | 2010-09-30 | 2011-09-29 | IMPROVED process for isomerizing HOPS-ALPHA ACIDS TO ISO ALPHA ACIDS |
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GBGB1016430.9A GB201016430D0 (en) | 2010-09-30 | 2010-09-30 | Improved method for isomerisation of hop alpha-acids to iso-alpha-acids |
GB1016430.9 | 2010-09-30 |
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EP (1) | EP2622060B1 (en) |
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AU (1) | AU2011310098B2 (en) |
BR (1) | BR112013006406A2 (en) |
CA (1) | CA2808980A1 (en) |
DK (1) | DK2622060T3 (en) |
ES (1) | ES2545130T3 (en) |
GB (1) | GB201016430D0 (en) |
MX (1) | MX2013002693A (en) |
NZ (1) | NZ607511A (en) |
PL (1) | PL2622060T3 (en) |
PT (1) | PT2622060E (en) |
RU (1) | RU2573635C2 (en) |
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Cited By (5)
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WO2015059148A1 (en) * | 2013-10-21 | 2015-04-30 | Ifast Nv | Method for extraction and dissolution of hop acids in aqueous media |
WO2015121360A3 (en) * | 2014-02-12 | 2015-10-22 | Ifast Nv | Method for extraction and dissolution of hop acids in aqueous media |
WO2016075308A1 (en) * | 2014-11-13 | 2016-05-19 | Ifast Nv | Process for producing a brewed beverage or for brewing a beer |
US9909088B2 (en) | 2010-09-30 | 2018-03-06 | Ifast Nv | Method for isomerisation of hop alpha-acids to iso-alpha-acids |
CZ308488B6 (en) * | 2019-07-09 | 2020-09-16 | Výzkumný ústav pivovarský a sladařský, a.s. | Preparation for simultaneous beer bittering and colouring, a method of its production and use |
Families Citing this family (1)
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US20170020165A1 (en) * | 2015-07-22 | 2017-01-26 | 48th Parallel Incorporated | Iso-alpha acid tinctures and carbonated beverage compositions including the same |
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US9909088B2 (en) | 2010-09-30 | 2018-03-06 | Ifast Nv | Method for isomerisation of hop alpha-acids to iso-alpha-acids |
WO2015059148A1 (en) * | 2013-10-21 | 2015-04-30 | Ifast Nv | Method for extraction and dissolution of hop acids in aqueous media |
CN105814184A (en) * | 2013-10-21 | 2016-07-27 | 公众有限责任公司 | Method for extraction and dissolution of hop acids in aqueous media |
US10392589B2 (en) | 2013-10-21 | 2019-08-27 | Ifast Nv | Method for extraction and dissolution of hop acids in aqueous media |
WO2015121360A3 (en) * | 2014-02-12 | 2015-10-22 | Ifast Nv | Method for extraction and dissolution of hop acids in aqueous media |
WO2016075308A1 (en) * | 2014-11-13 | 2016-05-19 | Ifast Nv | Process for producing a brewed beverage or for brewing a beer |
CN107109315A (en) * | 2014-11-13 | 2017-08-29 | 公众有限责任公司 | For producing brewed beverages or method for beer brewing |
RU2727676C2 (en) * | 2014-11-13 | 2020-07-22 | Ифаст Нв | Method of producing beer |
CZ308488B6 (en) * | 2019-07-09 | 2020-09-16 | Výzkumný ústav pivovarský a sladařský, a.s. | Preparation for simultaneous beer bittering and colouring, a method of its production and use |
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CA2808980A1 (en) | 2012-04-05 |
US9909088B2 (en) | 2018-03-06 |
AU2011310098A1 (en) | 2013-03-14 |
BR112013006406A2 (en) | 2017-11-14 |
RU2013108177A (en) | 2014-11-10 |
PT2622060E (en) | 2015-09-23 |
EP2622060B1 (en) | 2015-05-20 |
DK2622060T3 (en) | 2015-08-17 |
CN103180428B (en) | 2015-08-05 |
ES2545130T3 (en) | 2015-09-08 |
RU2573635C2 (en) | 2016-01-27 |
MX2013002693A (en) | 2013-06-07 |
AU2011310098B2 (en) | 2015-01-22 |
PL2622060T3 (en) | 2015-12-31 |
EP2622060A1 (en) | 2013-08-07 |
NZ607511A (en) | 2014-12-24 |
CN103180428A (en) | 2013-06-26 |
US20130209653A1 (en) | 2013-08-15 |
GB201016430D0 (en) | 2010-11-17 |
UA109671C2 (en) | 2015-09-25 |
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